Elastomer/aramid fiber dispersion

ABSTRACT

A process is disclosed for preparing a masterbatch composition of elastomer with a high concentration of aramid fibers, as the sole particulate component, distributed therethroughout.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to an elastomeric composition consistingessentially of an elastomer and a high concentration of aramid fiberswith no reinforcing filler or particulate additives. The composition isuseful as a masterbatch to facilitate the blending of aramid fibers intoelastomers. The invention also relates to a process for making theelastomeric composition.

2. Description of the Prior Art

U.S. Pat. No. 4,514,541, issued Apr. 30, 1985 on the application ofFrances, discloses a masterbatch composition of elastomer, aramid pulp,and reinforcing filler. Reinforcing filler materials are required andthey are combined with the pulp before dispersion of the pulp into anorganic solvent solution of the elastomer in order to facilitatedispersion of the pulp for the elastomer. This patent stands as ateaching that filler material is required for successful dispersion ofpulp into the elastomer.

U.S. Pat. No. 4,543,377, issued. Sep. 24, 1985 on the application ofCrossman, discloses a process for making a dispersion of pulp materialsin a polymer. The dispersion is made by blending an aqueous mixture ofthe pulp with an organic solvent solution of the polymer and removingthe water and organic solvent after the pulp transfers from the aqueousphase to the organic phase.

Great Britain Patent application 2,147,589-A, published May 15, 1985,discloses a composition comprising aramid pulp and rubbery polymer. Itis definitely stated that the composition cannot be made at pulpconcentrations greater than about 20 parts of fiber per 100 parts ofpolymer; and that a maximum of about 12 parts fiber per 100 parts ofpolymer is preferred.

SUMMARY OF THE INVENTION

The present invention provides a process for preparing a compositionconsisting essentially of elastomer with, as a sole particulatecomponent, short aramid fibers homogeneously distributed through-out,comprising the steps of; dissolving elastomer in organic solvent to makean elastomer solution, dispersing aramid fibers in the elastomersolution, and evaporating the organic solvent from the dispersion of thearamid fibers in the elastomer.

There is, also, provided a masterbatch composition consistingessentially of elastomer with, as a sole particulate component, aramidfibers homogeneously distributed uniformly throughout wherein the aramidfiber particles have an average length of about 0.1 to 6 millimeters andthe aramid fibers represent about 30 to 300 weight parts per hundredparts of elastomer.

DETAILED DESCRIPTION OF THE INVENTION

The masterbatch composition of this invention utilizes an unusually highconcentration of aramid fibers in the elastomer matrix. While it hasbeen well known to make compositions with low concentrations of fibersin the elastomer and well known to make compositions with higherconcentrations of fibers so long as a filler or partitioning materialwas used, it has not, before, been known to make masterbatchcompositions with high concentrations of fibers and no filler material.

Aramid fibers, as discussed herein relating to this invention, includearamid pulp and short aramid fibers known as floc. Aramid floc is madeby cutting continuous aramid fiber into short lengths from about 0.1 to6 millimeters. Aramid pulp is made by refining aramid fibers and has adistribution of lengths up to about 8 millimeters with an average lengthof about 0.1 to 4 millimeters. For practice of this invention, aramidpulp is preferred and the term pulp will be used hereinafter referringto both pulp and floc.

The elastomers which can be used in practice of this invention includeboth, natural rubber and synthetic rubbery compounds. Synthetic rubberycompounds can be any which are dissolved by common organic solvents andcan include, among many others, polychloroprene and sulfur-modifiedchloroprene, hydrocarbon rubbers, butadiene-acrylonitrile copolymers,styrene butadiene rubbers, chlorosulfonated polyethylene,fluoroelastomers, polybutadiene rubbers, polyisoprene rubbers, and thelike.

Organic solvents which can be used are any which safely and effectivelydissolve an amount of the elastomer necessary to yield a solution ofelastomer. Eligible solvents are aliphatic and aromatic, polar andnonpolar solvents, including, among many others, acetone, toluene,ethylmethylketone, hexane, cyclohexane, naphtha, and the like. A solventshould be used which will readily dissolve the elastomer, preferably butnot necessarily at temperatures of 15°-25° C. Smaller amounts of solventare preferred for facilitating removal of the solvent from thecomposition during preparation and for recovery of the solvent duringthe solvent removal.

This invention utilizes and is limited to aramid fibers which include,as a preferred material, aramid pulp. By aramid pulp is meant asynthetic pulp, for example, as made by mechanical shattering of fibersderived from high strength, high modulus aromatic polyamide fibers suchas those described in U.S. Pat. No. 3,869,429 and 3,869,430.Particularly preferred is aramid pulp derived from poly(p-phenyleneterephthalamide) fibers. Aramid pulp is preferably made using pulprefining methods similar to those of the paper industry. The aramidfibers are shattered both transversely and longitudinally to providefibers having a length which depends on the degree of refinement.Attached to these fibers are fine fibrils which have a diameter as smallas 0.1 micrometer as compared with a diameter of about 12 micrometersfor the main (trunk) part of the fiber. Aramid pulp particles have theappearance of hairy fibers.

Preparation of the composition of this invention is relatively simplebut is counter to the teachings of the prior art. First, an elastomerresin is dissolved in enough of the organic solvent to yield a completesolution. Generally, when compositions of 30 to 100 weight parts ofaramid pulp per hundred parts resin (phr) or thereabouts, are beingmade, the elastomer solution will have from 1 to 4 weight parts ofsolvent for each part of elastomer. When compositions of higher aramidpulp--say 200 to 300 phr--are being made, the elastomer solution couldhave 10 to as much as 20 weight parts of solvent for each part ofelastomer. The solution is prepared by conventional means using wellknown agitation or stirring forces and heat, as required or desired forany particular situation.

Once the solution is completed, the aramid pulp is added with agitationforces as necessary to afford complete dispersion of the individual pulpparticles. In pulp dispersion processes of the past, it was believedthat reinforcing filler or partitioning particles had to be combinedwith the pulp, as dispersing aids, before the pulp could be dispersed inthe elastomer, to accomplish complete dispersion of the pulp particles.It has now been discovered that such filler or partitioning particledispersing aids are not necessary-for complete dispersion. It should bemade clear that it is not necessary to wait for the elastomer to becompletely dissolved before dispersing the pulp in the solution. Thepulp can be added before the elastomer is completely dissolved; and caneven be combined with dry particles of the elastomer before adding thesolvent. As the solvent dissolves the elastomer, the pulp becomesdispersed in the elastomer solution. It should be emphasized that theelement of the present invention, which is believed to be novel andpatentable, is the, heretofore unrecognized, capability to achievesubstantially complete dispersion of aramid pulp without the use of anyother particulate materials to serve as aids in dispersing the pulp.

Once the pulp has been dispersed in the elastomer solution, the solventis evaporated from the dispersion, preferably, but not necessarily,under continued agitation forces. Removal of the solvent can befacilitated by heating the dispersion and using forced air or inert gasor by applying a vacuum. It is a surprising result of the process ofthis invention that the composition of elastomer and aramid pulpcrumbles to small particles as the solvent is driven out of the systemunder continued agitation forces. At relatively low aramid pulpconcentrations--like 20-30 phr--the composition crumbles into smallparticles; but at higher concentration--greater than about 50 phr--thecomposition forms into flakes and the composition particle size, whileclearly a function of the details of the process and the productcomposition, is small and quite manageable, on the order of a fewcentimeters in average diameter. The particles typically take the formof crumbs or flakes which vary in size from less than a centimeter toseveral centimeters, and more typically, from a centimeter to aboutthree centimeters in length. At aramid pulp concentrations of about 50to 150 phr, the particles are generally flake-like, having a thicknessof about 0.05 to 2 millimeters, more usually 0.1 to 0.6 millimeter, anda length to width (aspect) ratio of from about 1 to about 30. Generally,the particle size is smaller as the concentration of pulp in thecomposition is increased; and at pulp concentrations of greater thanabout 150 phr, the particles are generally less flake-like and morefibrous.

The crumb or flake nature of this product has been found to besurprising, unique, and quite useful. The thin flake-like particles areeasily dried, are easily handled and packaged and, in the high surfacearea flake form, are readily compounded with other elastomer materials.This product of the invention, in crumb or flake form, is ready forcompounding with other elastomers as a masterbatch. It should be notedthat at aramid pulp concentrations of greater than about 200 phr, thequality of dispersion is somewhat decreased.

While the masterbatch product of this invention consists essentially ofelastomer and aramid pulp, it may include small amounts ofnonparticulate additives such as plasticizers, tackifiers, stabilizers,cure agents, antioxidants and the like, which do not affect thedispersing of the aramid pulp in the elastomer.

An initial measure of quality in the product of this invention is in thehomogeneity of the aramid pulp elastomer dispersion. The homogeneity iseasily directly measured by observation of a sample of the compositionflattened under heat and pressure.

Dispersion Quality. To evaluate the degree of homogeneity of aramid pulpdispersion, a small sample of the composition (about 0.5 gram) is placedbetween thick plates and a pressure of about 100 megaPascals is applied.At that pressure, the sample is heated to 120° C. (250° F.), maintainedat that temperature for about five minutes, and then cooled to about 25C. The sample, flattened to an adequate thinness, can be observed withtransmitted light for quality of dispersion. A fully dispersed productexhibits no fiber clumps to the naked eye.

The actual value and effectiveness of the invention is measured by howwell the process of this invention facilitates the dispersion of aramidpulp in a final compound.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE 1

In the conduct of this example, aramid pulp was dispersed into solutionsof several elastomers and the quality of the dispersions was determined.

The elastomers were as follow:

A. "Nordel® 2522" (a sulfur-curable, low viscosity hydrocarbon rubbersold by E. I. du Pont de Nemours & Co.)

B. "Hypalon® 100" (a chlorosulfonated polyethylene sold by E. I. du Pontde Nemours & Co.).

C. "Neoprene GW" (a polychloroprene sold by E. I. du Pont de Nemours &Co.)

D. Natural Rubber

E. "PS 2400" (a silicone elastomer sold by Precision Silicone Co.).

F. "Viton® B-200" (a fluoroelastomer sold by E. I. du Pont de Nemours &Co.).

Solutions for all of the elastomers except the Natural Rubber and theViton® B-200 were made by dissolving 1 weight part of the elastomer into4 weight parts of the solvent. For the Natural Rubber, 1 weight part ofthe rubber was dissolved into 6 weight parts of the solvent; and, forthe Viton® B-200, 1 weight part of the elastomer was dissolved in 2weight parts of the solvent.

The aramid pulp used in this example was a pulp of poly(p-phenyleneterephthalamide) sold by E. I. du Pont de Nemours & Co. under thetradename Kevlar®, merge 6F543.

The desired amount of aramid pulp was dispersed into a portion of theelastomer solutions and the solvent was evaporated from the dispersion.The aramid pulp concentrations ranged from 35 to 100 weight parts perhundred weight parts of elastomer (phr) and the solvents were hexane,toluene and acetone, as indicated in Table 1. The compositions andresults of the dispersion are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Example  Elastomer    Solvent  Pulp Conc                                      ______________________________________                                        1-1      A            Hexane     35 phr                                       1-2      A            Hexane   50                                             1-3      A            Hexane   75                                             1-4      A            Hexane   100                                            1-5      A            Toluene  35                                             1-6      A            Toluene  50                                             1-7      A            Toluene  75                                             1-8      B            Toluene  75                                             1-9      C            Toluene  75                                              1-10    D            Toluene  75                                              1-11    E            Toluene  75                                              1-12    F            Acetone  35                                             ______________________________________                                    

In all of the dispersion tests described above, the Dispersion Qualitywas very good. All flattened samples of the dispersions revealedhomogeneous distribution of the aramid pulp throughout the elastomer.These compositions and other compositions of this invention find use asmasterbatch materials to be compounded with other elastomer componentsas a means for introducing a completely dispersed pulp component intoelastomer products.

When it is attempted to disperse aramid pulp into elastomers withoutdissolving the elastomer in solvent, the dispersion of pulp is unevenand incomplete with the pulp remaining in clumps.

The aramid pulp can be completely dispersed in the elastomers by meansof the prior art process wherein the pulp is first combined with afinely-divided reinforcing filler, such as carbon black and thecombination of pulp and filler is then blended with a solution of theelastomer. In that prior art process, however, the aramid pulpmasterbatch must always include a reinforcing filler; and, in thepresent invention, a masterbatch is made without the reinforcing fillerusing the aramid pulp as the only particulate material.

The present invention permits preparation of a masterbatch ofhomogeneously dispersed aramid pulp without the presence of, or the needfor, any other particulate material.

EXAMPLE 2

In order to investigate the Dispersion Quality of masterbatchcompositions of this invention at high concentrations of aramid pulp,the elastomer identified as Nordel® 2522 in EXAMPLE 1, the aramid pulpfrom EXAMPLE 1, and hexane as the solvent, were combined in the same wayas described in EXAMPLE 1 with concentrations of pulp and solventindicated in Table 2.

                  TABLE 2                                                         ______________________________________                                                 Solvent/               Dispersion                                    Example  Elastomer    Pulp Conc.                                                                              Quality                                       ______________________________________                                        2-1       6:1         150       Good                                          2-2       6:1         200       Good                                          2-3      10:1         200       Good                                          2-4      10:1         300       Fair                                          2-5      20:1         500       No                                            ______________________________________                                         "Good" means no fiber clumps;                                                 "Fair" means some fiber clumps; and                                           "No" means no light transmission.                                        

EXAMPLE 3

As a demonstration of the utility and effectiveness of the masterbatchof this invention, several of the compositions from EXAMPLES 1 and 2were compounded into elastomer samples and cured. The cured samples weretested and evaluated with regard to quality of the pulp dispersion.

The curable elastomer formulation was, as follows, with the amount ofmasterbatch adjusted to provide aramid pulp in an amount of 20 phr:

    ______________________________________                                               Component phr                                                          ______________________________________                                               Nordel ® 2522                                                                       80                                                                  Neoprene FB                                                                             20                                                                  "HiSil 233"                                                                             35.5                                                                Aramid pulp                                                                             20                                                                  Zinc oxide                                                                              5                                                                   Sulfur    1.5                                                                 MBT       1                                                                   Methyl tuads                                                                            0.5                                                                 Butyl zimate                                                                            2                                                            ______________________________________                                         "Neoprene FB" is a low viscosity chloroprene elastomer sold by E. I.          dupont de Nemours and Company.                                                "HiSil 233" is a precipitated silica sold by PPG, Inc.;                       "MBT" is 2mercaptobenzothiazole sold by R. T. Vanderbilt;                     "Methyl tuads" is Tetramethylthiuram Disulfide sold by R. T. Vanderbilt;      "Butyl zimate" is zinc dibutyldithiocarbamate sold by R. T. Vanderbilt.  

The compositions were mixed for 1-3 minutes at 200°-240° F. at low speedin a Banbury mixer, were further mixed on a 2-roll roll mill for 3-5minutes, and, then, were sheeted off at a thickness of about 2millimeters. Details of the compositions are presented in Table 3.

                  TABLE 3                                                         ______________________________________                                                  Masterbatch      Dispersion                                         Examples  Composition      Appearance                                         ______________________________________                                        3-1       1-1              Uniform                                            3-2       1-2              Uniform                                            3-3       1-3              Uniform                                            3-4       1-4              Uniform                                            3-5       2-1              Uniform                                            3-6       2-2              Nonuniform                                         3-7       2-3              Uniform                                            3-8       2-4              Uniform                                            3-9       2-5              Nonuniform                                         Control   --               Nonuniform                                         ______________________________________                                         .sup.1 "Uniform" means that there were no undispersed fibers.                 .sup.2 "Nonuniform" means that the compound was speckled with clumps of       undispersed pulp.                                                        

The control composition was made in the same manner as the others ofthis example, with the exception that the aramid pulp was disperseddirectly into the elastomer without the benefit of any masterbatchcomponent.

EXAMPLE 4

This example represents an additional demonstration of the effectivenessof the dispersion of this invention as a masterbatch composition. Forthis example, the elastomer was Neoprene GRT, a chloroprene sold by E.I. duPont de Nemours and Company.

A dispersion composition was made using an elastomer solution of 4weight parts toluene and 1 weight part elastomer, the pulp of EXAMPLE 1in an amount to yield 50 phr, and the procedure of this invention fromEXAMPLE 1.

That dispersion was compounded, by the procedure of EXAMPLE 3 at170°-220° F., in the following formulation, with the amount ofmasterbatch dispersion adjusted to provide aramid pulp in an amount of 5phr:

    ______________________________________                                        Component       phr                                                           ______________________________________                                        Neoprene GRT    100                                                           N 990 Black      45.5                                                         "Sundex 790"    10                                                            Zinc Oxide      5                                                             Aramid Pulp     5                                                             "Maglite D"     4                                                             AC PE 617A      3                                                             Octamine        2                                                             Stearic Acid    1                                                             ______________________________________                                         "N 990 Black" is carbon black sold by R. T. Vanderbilt;                       "Sundex 790" is aromatic oil (ASTM D 2226, Type 101), sold by R. E.           Carroll Corp.;                                                                "Maglite D" is magnesium oxide sold by Whitaker, Clark and Daniels;           "AC PE 617A" is a polyethylene processing aid sold by Allied Chemical;        "Octamine" is a mixture of octylated diphenyl and amine antioxidant sold      by R. T. Vanderbilt.                                                     

The control composition was made in the same manner as the compositionof the invention with the exception that the aramid pulp was disperseddirectly into the elastomer without the benefit of any masterbatchcomponent.

Aramid pulp in the composition of the invention was uniformly dispersedthroughout the elastomer with no clumps of pulp noticeable to the nakedeye. The control composition, on the other hand, was speckled withclumps of aramid pulp which were not uniformly dispersed in theelastomer.

EXAMPLE 5

In this Example, the composition identified as 1-7 from EXAMPLE 1 wascompounded as described in, and in accordance with the formulation of,EXAMPLE 3, and samples of the cured compositions were tested for breakstrength, modulus, and elongation at break.

There was a control which included no pulp and a comparison whichincluded 20 phr of aramid pulp compounded directly into the compositionwithout the benefit of any masterbatch component. Results of the testsare presented in Table 5.

                  TABLE 5                                                         ______________________________________                                                                       This                                                       Control Comparison Invention                                      ______________________________________                                        Machine Direction                                                             Modulus at 5% 131       1631       2164                                       Elongation (psi)                                                              Break Strength (psi)                                                                        1149      2104       2475                                       Elongation (%)                                                                              277        12          7                                        Cross machine Direction                                                       Modulus at 5% 119        216        352                                       Elongation (psi)                                                              Break Strength (psi)                                                                        998        888       1063                                       Elongation (%)                                                                              323        60         57                                        ______________________________________                                    

The Modulus, Break Strength, and Elongation tests were conducted inaccordance with ASTM D 412.

As shown in the examples, above, improved dispersion of the aramid pulp,yields improved physical properties for the compounded compositions.

I claim:
 1. A process for preparing a composition consisting essentiallyof flake-like particles of elastomer with, as a sole particulatecomponent, aramid fibers having an average length of 0.1 to 6millimeters in an amount from 30 to 300 weight parts of fibers perhundred parts of elastomer homogeneously distributed uniformlythroughout, wherein the flake-like particles have a thickness of about0.05 to 2 millimeters and an aspect ratio of 1 to 30, comprising thesteps of:a) dispersing aramid fibers in a solution of an elastomer in anorganic solvent having 1 to 20 weight parts of solvent for each part ofelastomer; and b) evaporating the organic solvent from the dispersion ofaramid fibers in elastomer under continued agitation forces.
 2. Theprocess of claim 1 wherein the elastomer is dissolved in the organicsolvent to make an elastomer solution before dispersing the aramidfibers in the solution.
 3. The process of claim 1 wherein the aramidfibers is combined with particles of the elastomer before adding theorganic solvent to dissolve the elastomer and disperse the aramidfibers.
 4. The process of claim 1 wherein the fibers are aramid pulp. 5.The process of claim 1 wherein the fibers are poly(p-phenyleneterephthalamide).